The preparation of titania (TiO2)/polyvinylidene fluoride (PVDF) composite hollow fiber membrane by phase transition process was introduced. The separation property, microstructure, thermal stability and crystalline phase of composite membranes were characterized by rejection experiment, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and X-ray diffraction (XRD), respectively. The results show that bovine serum albumin (BSA) rejection ratio and breaking stress of the composite membrane are 86.67% and 4.70 MPa, which are improved greatly compared to those 3.27% and 3.35 MPa of the pure PVDF membranes. Moreover the pore size and its distribution of the composite membrane characterized by nitrogen isothermal absorption measurement are smaller and narrower than those of the pure PVDF membranes'.